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We report here an electrolysis optical coherence tomography (eOCT) platform to visualize the chemical reactions occurring in a CO2 electrolyzer. The eOCT platform was designed to capture three dimensional images and videos at high spatial (~1 µm) and temporal (3 to reduce CO2 into CO at applied current densities of 50-800 mA cm−2. This video resolved the nucleation and formation of CO2 in the cathode compartment upon reaction of HCO3– with H+ delivered through the membrane, the formation of CO at the cathode|electrolyte interface, and H2 throughout the cathode compartment. The video captured the strikingly dynamic movement of the cathode and membrane components during electrolysis, and linked CO production to regions of the electrolyzer in which CO2 were in direct contact with both the membrane and the catalyst layers. This visualization enabled us to correlate the decrease in CO production to a buildup of CO2, CO, and H2, and (bi)carbonate salts at the cathode layer. The statistical analysis of phase distribution images allowed us to understand the competition between main (CO2 reduction) and side (hydrogen evolution) reactions in both time and space domains. We also show how a pulsing current liberates these residual bubbles and (bi)carbonates to recover CO production. These results highlight the power of using an eOCT platform to temporally and spatially resolve CO2RR electrolysis.

Electrocatalytic palladium membrane reactors (ePMRs) use electricity and water to drive hydrogenation reactions without forming H2 gas. In these reactors, a hydrogen-permeable palladium foil physically separates electrochemical proton generation in aqueous media from chemical hydrogenation in organic media. We report herein the use of the ePMR to electrolytically hydrogenate furfural, an important biomass derivative. This system was proven to convert furfural into furfuryl alcohol and tetrahydrofurfuryl alcohol with 84% and 98% selectivities, respectively. To reach these high selectivities, we designed and built an ePMR for high-throughput testing. Using this apparatus, we tested how different solvents, catalysts, and applied currents impacted furfural hydrogenation. We found that bulky solvents with weak nucleophilicities suppressed the formation of side products. Notably, these types of solvents are not compatible with standard electrochemical hydrogenation architectures where electrolysis and hydrogenation occur in the same reaction chamber. This work highlights the utility of the ePMR for selective furfural hydrogenation without H2 gas, and presents a possible pathway for helping to decarbonize the hydrogenation industry.

The aim of this retrospective study is to correlate the effect of a suburethral sling procedure and sling location based on ultrasound examination.This was a retrospective analysis of group of patients diagnosed with urodynamic stress incontinence that were later treated by single surgeon between 01/2009 and 10/2016. 4D volumes acquired at least three months postoperatively were analyzed. The gap between the sling and symphysis pubis (sling-pubis gap, SPG) on Valsalva was measured.The group comprises 378 patients, with a mean follow-up of 14.3 months. The success rate was 89.4%. The mean SPG on Valsalva was 12.0 mm (SD 2.5) in the cured group, whereas in the failure group the mean distance was on Valsalva 14.1 mm (SD 2.8) (P˂0.001).A smaller sling-pubis gap on translabial ultrasound imaging after suburethral sling surgery is associated with cure of stress urinary incontinence. This article is protected by copyright. All rights reserved.

An electrocatalytic palladium membrane reactor (ePMR) uses electricity and water to drive hydrogenation without H2 gas. The device contains a palladium membrane to physically separate the formation of reactive hydrogen atoms from hydrogenation of the unsaturated organic substrate. This separation provides an opportunity to independently measure the hydrogenation reaction at a surface without any competing H2 activation or proton reduction chemistry. We took advantage of this feature to test how different metal catalysts coated on the palladium membrane affect the rates of hydrogenation of C=O and C=C bonds. Hydrogenation occurs at the secondary metal catalyst and not the underlying palladium membrane. These secondary catalysts also serve to accelerate the reaction and draw a higher flux of hydrogen through the membrane. These results reveal insights into hydrogenation chemistry that would be challenging using thermal or electrochemical hydrogenation experiments.

We report here the direct hydrogenation of O

We report herein that sulfuric acid electrolyte affects the kinetics of hydrogen sorption and desorption, the amount of absorbed hydrogen, and the electrocatalytic activity of palladium using X-ray...

The deployment of electrolyzers that convert CO2 into chemicals and fuels requires appropriate integration with upstream carbon capture processes. To this end, the electrolytic conversion of aqueou...

Strain engineering can increase the activity and selectivity of an electrocatalyst. Tensile strain is known to improve the electrocatalytic activity of palladium electrodes for reduction of carbon dioxide or dioxygen, but determining how strain affects the hydrogen evolution reaction (HER) is complicated by the fact that palladium absorbs hydrogen concurrently with HER. We report here a custom electrochemical cell, which applies tensile strain to a flexible working electrode, that enabled us to resolve how tensile strain affects hydrogen absorption and HER activity for a thin film palladium electrocatalyst. When the electrodes were subjected to mechanically-applied tensile strain, the amount of hydrogen that absorbed into the palladium decreased, and HER electrocatalytic activity increased. This study showcases how strain can be used to modulate the hydrogen absorption capacity and HER activity of palladium.

Gas-fed CO2 electrochemical flow reactors are appealing platforms for the electrolytic conversion of CO2 into fuels and chemical feedstocks at commercially relevant current densities (≥100 mA/cm2)....

Here, we quantify the effect of an external magnetic field (β) on the oxygen evolution reaction (OER) for a cobalt oxide|fluorine-doped tin oxide coated glass (CoO

The highest performance flow cells capable of electrolytically converting CO2 into higher value chemicals and fuels pass a concentrated hydroxide electrolyte across the cathode. A major problem for CO2 electrolysis is that this strongly alkaline medium converts the majority of CO2 into unreactive HCO3– and CO32– rather than CO2 reduction reaction (CO2RR) products. The electrolysis of CO (instead of CO2) does not suffer from this same problem because CO does not react with hydroxide. Moreover, CO can be more readily converted into products containing two or more carbon atoms (i.e., C2+ products). While several solid-state electrocatalysts have proven competent at converting CO into C2+ products, we demonstrate here that molecular electrocatalysts are also effective at mediating this transformation in a flow cell. Using a molecular copper phthalocyanine (CuPc) electrocatalyst, CO was electrolyzed into C2+ products at high rates of product formation (i.e., current densities J ≥200 mA/cm2), and at high Faradaic efficiencies for C2+ production (FEC2+; 72% at 200 mA/cm2). These findings present a new class of electrocatalysts for making carbon-neutral chemicals and fuels.

Gas diffusion electrodes (GDEs) mediate the transport of reagents, products, and electrons in electrochemical reactors designed to reduce CO2 into fuels or chemicals. While the ratio of ionomer to electrocatalyst in the precursor catalyst ink is typically assumed not to change after being deposited on the GDE, we show herein that this assumption is likely not valid. Moreover, we discovered that the faradaic efficiency for formate, which is considered to be inconsequential relative to CO when using Ag electrocatalysts, can be modulated by 20% by a mere 5 wt% change in GDE Nafion® content. We were able to resolve these small differences in GDE composition by developing an X-ray fluorescence (XRF) spectroscopic protocol that quantifies the sulfonate groups appended to the polytetrafluoroethylene (PTFE) backbone of Nafion®. Using this protocol, we were able to determine how to precisely control the relative amount of ionomer to electrocatalyst for each GDE. We also found that maintaining a uniform ionomer–catalyst composition across the entire GDE can likely be done more effectively with automated spray coating than with manual deposition methods. We recommend following these procedures in order to generate reproducible CO2RR performance parameters in flow cells.

Useful materials must satisfy multiple objectives, where the optimization of one objective is often at the expense of another. The Pareto front reports the optimal trade-offs between these conflicting objectives. Here we use a self-driving laboratory, Ada, to define the Pareto front of conductivities and processing temperatures for palladium films formed by combustion synthesis. Ada discovers new synthesis conditions that yield metallic films at lower processing temperatures (below 200 °C) relative to the prior art for this technique (250 °C). This temperature difference makes possible the coating of different commodity plastic materials (e.g., Nafion, polyethersulfone). These combustion synthesis conditions enable us to to spray coat uniform palladium films with moderate conductivity (1.1 × 10

ObjectivesSpeckle-tracking echocardiography enables detection of abnormalities in cardiac mechanics with higher sensitivity than conventional measures of left ventricular (LV) dysfunction and may provide insight into the pathogenesis of coronary heart disease (CHD). We investigated the relationship of LV longitudinal strain, LV early diastolic strain rate (SR) and left atrial (LA) reservoir strain with long-term CHD incidence in community-dwelling older adults.MethodsThe association of all three strain measures with incidence of non-fatal and fatal CHD (primary outcome of revascularisation, non-fatal and fatal myocardial infarction) was examined in the population-based Cardiovascular Health Study using multivariable Cox proportional hazards models. Follow-up was truncated at 10 years.ResultsWe included 3313 participants (mean (SD) age 72.6 (5.5) years). During a median follow-up of 10.0 (25th–75th percentile 7.7–10.0) years, 439 CHD events occurred. LV longitudinal strain (HR=1.25 per SD decrement, 95% CI 1.09 to 1.43) and LV early diastolic SR (HR=1.31 per SD decrement, 95% CI 1.14 to 1.50) were associated with a significantly greater risk of incident CHD after adjustment for potential confounders. By contrast, LA reservoir strain was not associated with incident CHD (HR=1.06 per SD decrement, 95% CI 0.94 to 1.19). Additional adjustment for biochemical and echocardiographic measures of myocardial stress, dysfunction and remodelling did not meaningfully alter these associations.ConclusionWe found an association between echocardiographic measures of subclinically altered LV mechanics and incident CHD. These findings inform the underlying biology of subclinical LV dysfunction and CHD. Early detection of asymptomatic myocardial dysfunction may offer an opportunity for prevention and early intervention.

The electrolysis of carbon capture solutions bypasses energy-intensive CO

An electrocatalytic palladium membrane reactor (ePMR) uses electricity and water to drive hydrogenation without H

Introduction: Patients with HIV have an elevated risk of cardiovascular disease (CVD) that may be partially driven by inflammation and residual immune dysfunction despite treatment with antiretroviral therapy (ART). Coronary microvascular dysfunction (CMD) is an important pathophysiological link between inflammation, immune dysfunction, and CVD and may provide mechanistic insight into CVD risk among HIV+ patients. Methods: We recruited 3 groups of adults aged 40-80 years free of CVD: HIV with evidence of prior/current immunocompromise (n=17), HIV without immunocompromise (n=19), and HIV- controls. All HIV+ participants were on ART and had suppressed viral loads. All controls were on HIV pre-exposure prophylaxis (PrEP). Immunocompromise was defined as nadir CD4 count Results: Of 51 individuals who underwent CFR testing, median (IQR) age was 54 (46-58) and 92% were male. CFR was 3.71 (2.90-4.72) in controls, 3.49 (2.52-4.20) in HIV+/ immunocompromise-, and 2.35 (2.12-2.92) in HIV+/ immunocompromise+ (p=0.002). CMD was present in 7% of controls, 21% of HIV+/immunocompromise-, and 53% of HIV+/immunocompromise+ (p= 0.01). Compared with controls, HIV+/immunocompromise+ was significantly associated with lower CFR after multivariable adjustment ( Table ). Conclusions: HIV+ patients with current/prior immunocompromise free of CVD had high prevalence of CMD and had significantly lower CFR compared with controls on PrEP. Future studies should investigate CMD as a possible target for CVD prevention in HIV+ patients, particularly those with a prior or current immunocompromised state.

The highest performance flow cells capable of electrolytically converting CO2 into higher value chemicals and fuels pass a concentrated hydroxide electrolyte across the cathode. A major problem for CO2 electrolysis is that this strongly alkaline medium converts the majority of CO2 into unreactive HCO3– and CO32– rather than CO2 reduction reaction (CO2RR) products. The electrolysis of CO (instead of CO2) does not suffer from this same problem because CO does not react with hydroxide. Moreover, CO can be more readily converted into products containing two or more carbon atoms (i.e., C2+ products). While several solid-state electrocatalysts have proven competent at converting CO into C2+ products, we demonstrate here that molecular electrocatalysts are also effective at mediating this transformation in a flow cell. Using a molecular copper phthalocyanine (CuPc) electrocatalyst, CO was electrolyzed into C2+ products at high rates of product formation (i.e., current densities J ≥200 mA/cm2), and at high Faradaic efficiencies for C2+ production (FEC2+; 72% at 200 mA/cm2). These findings present a new class of electrocatalysts for making carbon-neutral chemicals and fuels.

An autonomous laboratory for thin film discovery is used to optimize the doping and annealing of organic semiconductors., Discovering and optimizing commercially viable materials for clean energy applications typically takes more than a decade. Self-driving laboratories that iteratively design, execute, and learn from materials science experiments in a fully autonomous loop present an opportunity to accelerate this research process. We report here a modular robotic platform driven by a model-based optimization algorithm capable of autonomously optimizing the optical and electronic properties of thin-film materials by modifying the film composition and processing conditions. We demonstrate the power of this platform by using it to maximize the hole mobility of organic hole transport materials commonly used in perovskite solar cells and consumer electronics. This demonstration highlights the possibilities of using autonomous laboratories to discover organic and inorganic materials relevant to materials sciences and clean energy technologies.

Organic molecular hole-transport materials (HTMs) are appealing for the scalable manufacture of perovskite solar cells (PSCs) because they are easier to reproducibly prepare in high purity than polymeric and inorganic HTMs. There is also a need to construct PSCs without dopants and additives to avoid formidable engineering and stability issues. We report here a power conversion efficiency (PCE) of 20.6% with a molecular HTM in an inverted (p–i–n) PSC without any dopants or interlayers. This new benchmark was made possible by the discovery that, upon annealing, a spiro-based dopant-free HTM (denoted DFH) containing redox-active triphenyl amine (TPA) units undergoes preferential molecular organization normal to the substrate. This structural order, governed by the strong intermolecular interactions of the DFH dioxane groups, affords high intrinsic hole mobility (1 × 10−3 cm2 V−1 s−1). Annealing films of DFH also enables the growth of large perovskite grains (up to 2 μm) that minimize charge recombination in the PSC. DFH can also be isolated at a fraction of the cost of any other organic HTM.

Tunable and highly conductive hole transport materials are crucial for the performance of organic electronics applications such as organic light emitting diodes and perovskite solar cells. For commercial applications, these materials' requirements include easy synthesis, high hole mobility, and highly tuned and compatible electronic energy levels. Here, we present a systematic study of a recently discovered, easy-to-synthesize class of spiro[fluorene-9,9′-xanthene]-based organic hole transport materials. Systematic side group functionalization allows us to control the HOMO energy and charge carrier mobility. Analysis of the bulk simulations enables us to derive design rules for mobility enhancement. We show that larger functional groups (e.g. methyl) decrease the conformational disorder due to steric effects and thus increase the hole mobility. Highly asymmetric or polar side groups (e.g. fluorine), however, increase the electrostatic disorder and thus reduce the hole mobility. These generally applicable design rules will help in the future to further optimize organic hole transport materials.

Electrolytic palladium membrane reactors offer a means to perform hydrogenation chemistry utilizing electrolytically produced hydrogen derived from water instead of hydrogen gas. While previous embodiments of these reactors employed thick (≥25 μm) palladium foil membranes, we report here that the amount of palladium can be reduced by depositing a thin (1–2 μm) layer of palladium onto a porous polytetrafluoroethylene (PTFE) support. The supported palladium membrane can be designed to ensure the fast diffusion of reagent and hydrogen to the palladium layer. The hydrogenation of 1-hexyne, for example, shows that the supported Pd/PTFE membrane can achieve reaction rates (e.g., 0.71 mmol h−1) which are comparable to 0.92 mmol h−1 measured for palladium membranes with a high-surface area palladium electrocatalyst layer. The root cause of these comparable rates is that the high porosity of PTFE enables a 12-fold increase in electrocatalytic surface area compared to planar palladium foil membranes. These results provide a pathway for designing a cost-effective and potentially scalable electrolytic palladium membrane reactor.

Summary Commercially available electrochromic (EC) windows are based on solid-state devices in which WO3 and NiOx films commonly serve as the EC and counter electrode layers, respectively. These metal oxide layers are typically physically deposited under vacuum, a time- and capital-intensive process when using rigid substrates. Herein we report a facile solution deposition method for producing amorphous WO3 and NiOx layers that prove to be effective materials for a solid-state EC device. The full device containing these solution-processed layers demonstrates performance metrics that meet or exceed the benchmark set by devices containing physically deposited layers of the same compositions. The superior EC performance measured for our devices is attributed to the amorphous nature of the NiOx produced by the solution-based photodeposition method, which yields a more effective ion storage counter electrode relative to the crystalline NiOx layers that are more widely used. This versatile method yields a distinctive approach for constructing EC windows., Graphical Abstract, Highlights • Amorphous WO3 and NiOx films are produced by a solution-deposition method • The WO3 and NiOx films are assembled into a solid-state electrochromic device • The solid-state device exhibits state-of-the-art electrochromic performance • Amorphous NiOx is a superior counter electrode material compared with crystalline NiOx, Materials Science; Coatings; Energy Materials

We report here an electrochemical method for precise and accurate quantification of hydrogen absorption in palladium materials. We demonstrate that conventional chronocoulometry over-reports adsorbed hydrogen due to charge from the accompanying hydrogen oxidation reaction (HOR). We designed and built a bespoke electrochemical flow cell that mitigates the concurrent HOR reaction and consequently provides improved accuracy and reproducibility relative to other existing electrochemical techniques. The efficacy of this technique is demonstrated experimentally for a series of palladium sample types: a 100 nm electron-beam deposited thin film, a 20 μm electrodeposited palladium film, a casting of 21 nm edge-length cubic nanoparticles, and a casting of 27 nm edge-length octahedral nanoparticles. We contend that this method is the most effective for measuring hydrogen uptake in different palladium samples.

This article considers the results of the study of the titanium VT1-0 surface degradation (Grade-4 equivalent) for recrystallized- and ultrafine-grained states after fatigue testing. Comparative analysis of peculiarities of the titanium samples degradation was performed after coating formation by Micro-Arc Oxidation. It was found, that the coating formed by Micro-Arc Oxidation shows different degradation behaviors for recrystallized and ultrafine-grained states

The purpose of this two-part study is to model the effects of large penetrations of offshore wind power into a large electric system using realistic wind power forecast errors and a complete model of unit commitment, economic dispatch, and power flow. The chosen electric system is PJM Interconnection, one of the largest independent system operators in the U.S. with a generation capacity of 186 Gigawatts (GW). The offshore wind resource along the U.S. East Coast is modeled at five build-out levels, varying between 7 and 70 GW of installed capacity, considering exclusion zones and conflicting water uses. This paper, Part I of the study, describes in detail the wind forecast error model; the accompanying Part II describes the modeling of PJM's sequencing of decisions and information, inclusive of day-ahead, hour-ahead, and real-time commitments to energy generators with the Smart-ISO simulator and discusses the results. Wind forecasts are generated with the Weather Research and Forecasting (WRF) model, initialized every day at local noon and run for 48 h to provide midnight-to-midnight forecasts for one month per season. Due to the lack of offshore wind speed observations at hub height along the East Coast, a stochastic forecast error model for the offshore winds is constructed based on forecast errors at 23 existing PJM onshore wind farms. PJM uses an advanced, WRF-based forecast system with continuous wind farm data assimilation. The implicit (and conservative) assumption here is that the future forecast system for offshore winds will have the same performance as the current PJM's forecast system for onshore winds, thus no advances in weather forecasting techniques are assumed. Using an auto-regressive moving-average (ARMA) model, 21 equally-plausible sample paths of wind power forecast errors are generated and calibrated for each season at a control onshore wind farm, chosen because of its horizontally uniform landscape and large size. The spatial correlation between pairs of onshore wind farms is estimated with an exponential function and the matrix of error covariance is obtained. Validation at the control farm and at all other onshore farms is satisfactory. The ARMA model for the wind power forecast error is then applied to the offshore wind farms at the various build-out levels and combined with the matrix of error covariance to generate multiple samples of forecast errors at the offshore farms. The samples of forecast errors are lastly added to the WRF forecasts to generate multiple samples of synthetic, onshore-based, actual offshore wind power for use in Part II.

Whole-body magnetic resonance imaging (WB-MRI) is a radiation-free alternative to the1256 eligible WB-MRI scans were analyzed retrospectively with a single inclusion criterion, a clinical 12-month follow-up or a biopsy as ground truth. N = 285 patients received both a WB-MRI and a BS within 12 months. All the patients were imaged with a coronal T1w and a STIR, and n = 528 (42%) received an additional T1w-mDixon with gadoteridol (0.1 mmol Gd-DTPA/kg).From 1256 eligible patients, n = 884 (70%) had breast cancer as a primary disease, n = 101(8%) prostate cancer, and n = 77(6%) lung cancer. The sensitivity (Se) and negative predictive value (NPV) of the WB-MRI was 98/99%, significantly higher compared to BS with 82/89%, P 0.001 Mc Nemar's test. The specificity (Spe) and positive predictive value (PPV) of the WB-MRI and BS was 85/82% and 91/86%, respectively. The interobserver agreement between WB-MRI and BS was 71%, Cohen's kappa 0.42. Analysis of the added diagnostic value of gadolinium revealed Se/Spe/PPV/NPV of 98/93/92/98% for the NE WB-MRI and 99/93/85/100% for the WM-MRI + Gd, P 0.05 binary logistic regression with Fischer's exact test.WB-MRI exceeds the sensitivity of BS without compromising the specificity, even after omitting the gadolinium enhancer.

Chemical delithiation is used to prepare bulk quantities of amorphous silicon powder from lithium-silicon compounds. The amorphous silicon materials formed are air and water stable and are found to have layered structures. When cycled in Li-ion half cells, coatings containing layered amorphous silicon are found to have significantly lower volume expansion during lithiation and improved cycling characteristics compared to that of bulk crystalline Si. We suggest chemical delithiation as a convenient method to synthesize bulk quantities of Si powders containing self-organized void spaces that can accommodate volume expansion during lithiation.

It was found that the fatigue properties of submicrocrystalline titanium are significantly higher than those for its coarse-grained state. The application of the oxide coating leads to a slight increase in these properties for titanium with a submicrocrystalline and coarse-grained structure. Some features of fatigue fracture of submicrocrystalline and coarse-grained titanium are analyzed.

We evaluated effects of the school-based intervention "FIFA 11 for Health" for Europe on health and fitness profile in 10- to 12-year-old Faroese schoolchildren. 392 fifth-grade children were randomized into a control group (CG: n = 100, 11.1 ± 0.3 years, 149.0 ± 6.7 cm, 42.4 ± 10.2 kg) and an intervention group (IG: n = 292, 11.1 ± 0.3 years, 150.6 ± 6.9 cm, 44.2 ± 9.4 kg). IG underwent an 11-week intervention in which 2 weekly sessions of 45 minutes were included in the school curriculum focusing on health aspects, football skills, and 3v3 small-sided games. CG continued with their regular activities. Body composition, blood pressure, and resting heart rate, as well as Yo-Yo intermittent recovery children's test (YYIR1C) performance, horizontal jumping ability and postural balance were assessed pre and post intervention. Systolic blood pressure decreased more (-2.8 ± 9.9 vs 2.9 ± 8.4 mm Hg, P < .05) in IG than in CG. Lean body mass (1.0 ± 1.7 vs 0.7 ± 1.6 kg), postural balance (0.3 ± 3.9 vs -1.2 ± 5.9 seconds) and horizontal jump performance (5 ± 9 vs -5 ± 10 cm) increased more (P < .05) in IG than in CG. YYIR1C performance improved in CG (17%, 625 ± 423 to 730 ± 565 m) and IG (18%, 689 ± 412 vs 813 ± 391 m), but without between-group differences. A within-group decrease from 23.1 ± 8.4 to 22.5 ± 8.3% (P < .05) was observed in body fat percentage in IG only. In conclusion, the "FIFA 11 for Health" for Europe program had beneficial effects on SBP, body composition, jump performance and postural balance in 10- to 12-year-old Faroese schoolchildren, supporting the notion that school-based football interventions can facilitate health of children in a small-scale society and serve as an early step in the prevention of non-communicable diseases.